Preparation of nitrates of monohydric aliphatic alcohols



UNITED STATES PAT PREPARATION OF NITRATES OF MONOHY- DRIC ALIPHATIC ALCOHOLS Joseph A. Wyler, Allentown, Pa., assignor to Trojan Powder Company, Allentown, Pa.

T ()FFICE No Drawing. Application September 19, 1936, Serial No. 101,613

6 Claims. (Cl. 260144) My invention relates to a process for nitrating separate from its water wash and is then essenmonohydric aliphatic alcohols and particularly tially a mixture of nitrated ethyl lactate and deals with the nitration of monohydric aliphatic methyl nitrate. The yield is 309 parts. alcohols in the presence of esters of aliphatic monohydroxy carboxylic acids. The principal ob- EXAMPLE 2 V 5 ject of my invention is to provide improved means Buiyl lactate and pr w alcohol of prleparing nitrates of monohydric aliphatic al- 600 parts of a mixed acid consisting of 40% coho s.

nitric acid and 60% sulphuric acid are placed in It 15 Well known that mtnc acld reacts Wlth a suitable nitrator, cooled to about 20 C. or less,

1o methyl ethyl propyl' butyl and amyl alcohols to stirred and 200 parts of a mixture consisting of form nitrates. However, no really satisfactory 50 parts ethyl lactate, and 150 parts n propy1 method for carrying out this reaction between alcohol are added slowly maintaining the nitric acid and any of these alcohols to form the perature below for t main portion of the corresponding nitrates has ever been developed. mtmtmn The mixture is stirred about one hour The yields of nitrated products are low and the after an of the liquid to be nitrated has been 15 operations i too dangemllsadded, allowedto run into a separator, where the I p dlscovered i If a spent acid forms the lower layer and the nitrated phatic alcohol containing less than SIX carbon product the upper layer. The upper layer is run atoms be mlxed' Wlth ethyl lactate methyl into a relatively large amount of water, stirred,

tate propyl p butyl lactate amyl i i or separated by settling, washed with a dilute alkali the correspondmg glyconatfis that h mtratlon solution until all free acid has been neutralized the almhqls can be earned out Wlth excellent and then washed with water in order to remove ylelds f wllih f L the alkali. The final, neutral product is allowed nlifmtmg acld. I may use m of to separate from its water wash and is then essenphuric acid and nitric acid, or am1xture of nitr c many a mixture of nitrated ethyl lactate, and 25 acid and phosphoric acid or I may use n1tr1c acid prowl nitrate The yield is 277 parts alone without the additlon of any dehydrating agent. EXAMPLE No. 3

The general mode of operation is to mix the ali- Buiyl Lactate and butyl alcohol phatic alcohol with the aliphatic hydroxy acid u 30 ester in any proportion desired and then to add 1500 F of a mlXed fi conslstlng 0f this mixture to the nitrating acid" nitric acid and 60% sulphuric acid are placed 1n 2. The following examples how more how I suitable nitrator, COOled to about 20 C. or less, may carry out my process of it stirred and 500 parts of a mixture consisting of 200 parts butyl lactate and 300 parts butyl alcohol 35 EXAMPLE No. 1 are added slowly, maintaining the temperature Ethyl t t and methyl alcohol below 20 C. for the main portion of the nitration.

The mixture is stirred about one hour after all of 600 parts of a mlxed acld conslstmg of 40% the liquid to be nitrated has been added, allowed nitric acid and 60% sulphuric acid are placed in a to run into a Separator, Where the spent acid 40 suitable nitrator, cooled to about 20 C. or less, for the lower layer the nitrated product stirred, and 200 parts of a mixture consisting of 50 the upper 1 1 The upper layer is run into a Parts ethyl lactate and 150 parts methyl 811001101 relatively large amount of water, stirred, sepaare added S owly, maintaining the temperature rated by settling, washed with a dilute alkali solubelow 0 C- for the main Portion of the nitration tion until all free acid has been neutralized and 45 The mixture is stirred for about one hour after all then washed th water in order t remove t of the liquid to be nitrated has been d d. alkali. The final, neutral product is allowed to lowed to run into a separator, where the spent separate from its water wash and is then essenacid forms the lower layer a d the ated prodtially a mixture of nitrated butyl lactate and not the upper layer. The upper layer is run into butyl nitrate. The yield is 690 parts. 50 a relatively large amount of water, stirred, sepa- The examples given show the preferred embodirated by settling, washed with a dilute alkali soluments of my invention, and are merely illustrative tion until all free acid has been neutralized and of my process. Imay vary the strengths and prothen washed with water in order to remove the portions of acids used in nitrating, the tempera- 65 alkali. The final, neutral product is allowed to ture of nitration, the method of adding the liquids to be nitrated and other operative details which may be advisable under individual conditions, without departing from the essence of this invention.

It should be noted that although my examples do not mention the use of the glycollates I may use such glycollates as methyl glycollate, ethyl glycollate, propyl glycollate, butyl glycollate and amyl glycollate interchangeably with the lactates, the said glycollates performing all the functions performed by the corresponding lactates,

The finished nitrated product consists essentially of the nitrated alcohol, the nitrated ester of the hydroxy aliphatic carboxylic acid and a small percentage of the unnitrated alcohol started out with. This nitrated product may be used directly in explosives or it may be used as a source of methyl nitrate, ethyl nitrate, etc. which are readily separated by fractional distillation. Certain other particular uses for the mixed nitrates made by my process are as an ingredient of tetranitromethane explosives, plastic explosives, gelatin and waterproof explosives, and as a constitutent of fuels for automotive purposes.

I claim:

1. The process which comprises nitrating a monohydric aliphatic alcohol of less than 6 carbon atoms in the presence of an alkyl ester of a monohydroxy aliphatic carboxylic acid.

2. Theprocess which comprises nitrating a monohydric aliphatic alcohol of less than 6 carbon atoms in the presence of a nitrated alkyl ester of a monohydroxy aliphatic carboxylic acid.

3. The process which comprises nitrating a monohydric aliphatic alcohol of less than 6 car bon atoms in the presence of a nitrated alkyl ester of a monohydroxy aliphatic carboxylic acid, said alkyl being a member of the group consisting of the methyl, ethyl, propyl, butyl and amyl roups.

4. The process which comprises nitrating a monohydric aliphatic alcohol of less than 6 carbon atoms in the presence of an ester of a monohydroxy aliphatic carboxylic acid, at a temperature of less than 20 C.

5. The process which comprises nitrating a mixture of a monohydric aliphatic alcohol of less than 6 carbon atoms and an alkyl ester of a monohydroxy aliphatic carboxylic acid, said mixture containing a substantial proportion of the monohydric aliphatic alcohol by allowing said mixture to flow into a mixed acid consisting of approximately HNO3 and H2804, at a temperature less than 20 C. separating the nitrated product from the spent acid, washing and purifying said nitrated product,

6. The process which comprises nitrating a mixture of a monohydric aliphatic alcohol of less than 6 carbon atoms and a nitrated alkyl ester of a monohydroxy aliphatic carboxylic acid, said mixture containing a substantial proportion of monohydric aliphatic alcohol, by allowing said mixture to flow into a mixture comprising nitric acid and a dehydrating agent, at a temperature less than 20 (3., separating the nitrated product from the spent acid and washing and purifying said nitrated product.

JOSEPH A. WYLER. 

